CN112768834A - Method for preparing polyacrylonitrile/sulfonated polyether ether ketone lithium-sulfur battery diaphragm material by electrostatic spinning - Google Patents
Method for preparing polyacrylonitrile/sulfonated polyether ether ketone lithium-sulfur battery diaphragm material by electrostatic spinning Download PDFInfo
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- CN112768834A CN112768834A CN201911003234.0A CN201911003234A CN112768834A CN 112768834 A CN112768834 A CN 112768834A CN 201911003234 A CN201911003234 A CN 201911003234A CN 112768834 A CN112768834 A CN 112768834A
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Abstract
The invention discloses a preparation method of a lithium-sulfur battery diaphragm, which comprises the following steps: (1) putting polyether-ether-ketone and concentrated sulfuric acid into a container, heating in a water bath for several hours, pouring the solution into ice water to obtain sulfonated polyether-ether-ketone, washing the sulfonated polyether-ether-ketone to be neutral, and drying the sulfonated polyether-ether-ketone for later use; (2) adding polyacrylonitrile powder into an organic solvent, stirring to obtain a polyacrylonitrile solution, adding the sulfonated polyether ether ketone prepared in the step (1) into the organic solvent, mixing the polyacrylonitrile solution and the sulfonated polyether ether ketone solution, and stirring uniformly to obtain an electrostatic spinning solution; (3) carrying out electrostatic spinning on the obtained electrostatic spinning solution, and then drying and carrying out hot pressing treatment; (4) preparing a chitosan solution and a carboxylated carbon nanotube aqueous solution, and carrying out layer-by-layer self-assembly on the film obtained in the step (3). Compared with the prior art, the invention improves the thermal stability of the material, effectively inhibits the shuttling of polysulfide by introducing sulfonic acid groups, and prolongs the cycle life of the polysulfide.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur battery diaphragms, relates to a lithium-sulfur battery diaphragm and a preparation method thereof, and particularly relates to a method for preparing a polyacrylonitrile/sulfonated polyether ether ketone lithium-sulfur battery diaphragm material by electrostatic spinning.
Background
The lithium-sulfur battery as a novel environment-friendly battery has the advantages of high capacity (the specific capacity can reach 1650mAh/g), rich elemental sulfur reserve of active substances, low cost and the like, and attracts people's attention. However, the lithium sulfur battery has problems such as large volume expansion of the electrode during the cycle, poor conductivity of sulfur, and shuttle effect caused by polysulfide which is easily dissolved in the electrolyte generated during the redox reaction, resulting in a great loss of active materials, resulting in rapid capacity reduction, shortened cycle life of the battery, and severe limitation of its application.
The diaphragm plays an important role in the battery, can isolate the positive and negative electrodes of the battery to prevent the battery from short circuit, improves the safety performance of the battery, has certain liquid absorption and retention capacity on electrolyte, and reduces the internal resistance of the battery. The separator of the currently commercialized lithium-sulfur battery is a polyolefin-based separator, such as a polypropylene (PP) and Polyethylene (PE) microporous membrane, which has low economic cost, good electrochemical stability, high mechanical strength, and ideal pore size distribution, and thus is widely used. However, the polyolefin separator has poor electrolyte wettability, heat is released during the charging and discharging processes of the battery, and particularly at high temperature, the heat resistance of the film is poor, and the film is easy to shrink and degrade, so that internal short circuit of the electrode is caused.
Sulfonated polyether ether ketone (SPEEK) has excellent mechanical strength and thermal stability, meanwhile, sulfonate ions can form an ionic cluster aggregation phase of hydrophilic protons, a carbon skeleton can form an oleophilic micro-phase structural area, and a transition phase is formed between the two micro-phase structural areas. When the polymer is used as a lithium-sulfur battery separator, the aggregated sulfonic acid groups can form spherical micelles to serve as lithium ion conduction channels, and Sn 2-cannot pass through the spherical micelles, so that ion selectivity is realized. Polyacrylonitrile (PAN)/SPEEK is used as a matrix, electrostatic spinning and a layer-by-layer self-assembly technology are combined to prepare a fiber membrane, a compact functional layer is constructed on the surface, an ion transmission channel is formed by a sulfonic acid group introduced into the functional layer, ion selective permeation and lithium ion conduction are realized, a shuttle effect caused by permeation of polysulfide ions is inhibited, and the cycle life and the safety performance of the lithium-sulfur battery are expected to be improved.
Disclosure of Invention
Aiming at poor cycling stability of the lithium-sulfur battery, the invention aims to solve the problems that a fiber composite membrane prepared by an electrostatic spinning method is introduced with sulfonic acid groups to realize ion selective conduction, and a surface functional layer is constructed by combining layer-by-layer self-assembly, so that the barrier efficiency of the composite membrane material to polysulfide anions is further enhanced, and the cycling stability of the lithium-sulfur battery is improved.
The specific technical scheme of the invention is as follows:
the invention discloses a preparation method of a lithium-sulfur battery diaphragm, which comprises the following steps:
(1) putting polyether ether ketone (PEEK) and concentrated sulfuric acid into a container, heating in a water bath for several hours, pouring the reacted solution into ice water to obtain threadlike sulfonated polyether ether ketone (SPEEK), then washing with water until the solution is neutral, and drying for later use;
(2) dissolving Polyacrylonitrile (PAN) in an organic solvent, stirring at room temperature to form a uniform and stable spinning solution, dissolving sulfonated polyether ether ketone in the step (1) in the organic solvent, stirring at room temperature to form a uniform solution, mixing the two solutions, and continuously stirring until a uniform spinning solution is formed;
(3) weighing 5-15mL of spinning solution in an injector, placing the injector on a bracket of an electrostatic spinning machine, selecting a high-speed roller as a receiving device, winding a layer of aluminum foil on the roller for receiving polyacrylonitrile/sulfonated polyether ether ketone fibers, connecting a syringe needle with the anode of a high-voltage power supply through a lead, connecting the roller with the cathode of the high-voltage power supply, moving a platform at a distance of 15-25cm, a voltage of 18-24KV, an injection speed of 0.5-2mL/h, a roller rotating speed of 100-150rpm, and a receiving distance of 20-22 cm;
(4) taking the electrostatic spinning polyacrylonitrile/sulfonated polyether ether ketone fiber membrane off a roller, drying in a vacuum oven to obtain a primary spinning membrane, and then carrying out hot pressing treatment under a universal testing machine;
(5) preparing a chitosan solution and a carboxylated carbon nanotube aqueous solution, and performing a soaking method on the membrane obtained in the step (4) in the chitosan solution and the carboxylated carbon nanotube aqueous solution respectively to obtain the battery diaphragm by layer-by-layer self-assembly.
Preferably, the mass ratio of the polyether-ether-ketone and the concentrated sulfuric acid in the step (1) is 1: 7-1: 9.
Preferably, the temperature of the water bath heating in the step (1) is 60-80 ℃.
Preferably, the water bath heating time of the step (1) is 2-6 h.
Preferably, the organic solvent in the step (2) is one or more of N-N Dimethylformamide (DMF), N-N dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and Tetrahydrofuran (THF).
Preferably, the polyacrylonitrile in the step (2) accounts for 8-12 wt% of the solution, the sulfonated polyether ether ketone accounts for 15-25 wt% of the solution, and the two solutions are mixed according to the mass ratio of the polyacrylonitrile to the sulfonated polyether ether ketone being 90% -10% -50% to 50%.
Preferably, the spinning time in the step (3) is 1-10 hours, the spinning temperature is 20-50 ℃, the humidity is 20% -50%, and the diameter of a roller is 15-25 cm.
Preferably, the drying temperature in the step (4) is 40-100 ℃, the hot pressing temperature is 60-100 ℃, the pressure is 3-10 Mpa, and the hot pressing time is 1-30 min.
Preferably, the chitosan solution solvent in step (5) is one or a mixture of an acetic acid solution, a hydrochloric acid solution and a sulfuric acid solution.
Preferably, the number of the assembly layers in the step (5) is 0-20.
The invention has the beneficial effects that:
1. the film prepared by the method of electrostatic spinning and layer-by-layer self-assembly has good mechanical property, excellent porosity and liquid absorption rate.
2. The film prepared by the preparation method disclosed by the invention has excellent high temperature resistance, has no obvious shrinkage in size at a high temperature of 150 ℃, is good in thermal stability, is beneficial to facing sudden heat change in the charge and discharge processes of the battery, and improves the safety of the battery.
3. Polar groups such as sulfonic groups, amino groups, carboxyl groups and the like introduced into the film prepared by the method have good wettability on electrolyte of a lithium-sulfur battery.
4. The film prepared by the preparation method provided by the invention effectively inhibits the shuttle effect of polysulfide and prolongs the cycle life of the film.
Drawings
FIG. 1 is an SEM photograph of the film prepared in example 1 after hot pressing.
Fig. 2 is an SEM photograph of the 5-layer assembly layer prepared in example 1.
FIG. 3 is a 100-cycle plot of the film prepared in example 1 and PP at 0.1C.
FIG. 4 is an SEM photograph of the thin film prepared in example 2 before hot pressing
Fig. 5 is an SEM photograph of the 10 assembled layers prepared in example 2.
FIG. 6 is a 100-cycle plot of the film prepared in example 2 and PP at 0.1C.
FIG. 7 is an SEM photograph of the hot-pressed thin film prepared in example 3.
Fig. 8 is an SEM photograph of the 15 assembled layers prepared in example 3.
FIG. 9 is a 100 cycle plot of the film prepared in example 3 and PP at 0.1C.
Detailed Description
Example 1
Weighing 10g of PEEK and 70mL of concentrated sulfuric acid, heating in a water bath at 60 ℃ for 6 hours, pouring the reacted solution into ice water to obtain threadlike sulfonated polyether ether ketone (SPEEK), then washing with water until the solution is neutral, and drying for later use; mixing 5mLN-N dimethylformamide and 5mLN-N dimethylacetamide solvents, dissolving 1.2g of PAN powder in a beaker to prepare a PAN solution with the mass fraction of 12% wt, mixing 5mL of N-N dimethylformamide and 5mLN-N dimethylacetamide solvents to dissolve 2g of SPEEK powder in the beaker to prepare a SPEEK solution with the mass fraction of 20% wt, measuring 5mL of PAN solution and 5mL of SPEEK solution in the beaker, uniformly stirring to form a uniform solution, measuring 10mL of spinning solution in a syringe, placing the syringe on a bracket of an electrostatic spinning machine, selecting a high-speed roller as a receiving device, winding a layer of aluminum foil on the roller to receive polyacrylonitrile/sulfonated polyether ether ketone fibers, connecting a syringe needle with a positive pole of a high-voltage power supply through a lead, connecting the roller with a negative pole of the high-voltage power supply, the platform moving distance is 23cm, the voltage is 18KV, the injection speed is 1mL/h, the roller rotating speed is 150rpm, the receiving distance is 21cm, the spinning time is 6 hours, the spinning temperature is 25 ℃, the humidity is 40%, the roller diameter is 23cm, the electrospun polyacrylonitrile/sulfonated polyether ether ketone fiber membrane is taken down from the roller, the electrospun polyacrylonitrile/sulfonated polyether ether ketone fiber membrane is obtained after drying treatment in a vacuum oven at 60 ℃ and then hot pressing treatment is carried out under a universal tester, the hot pressing temperature is 60 ℃, the pressure is 5MPa, the time is 1min, 2% o chitosan acetic acid solution and 2% carboxylated carbon nanotube aqueous solution are prepared, and the battery diaphragm is obtained by carrying out 5-layer-by-layer self-assembly on the hot pressed membrane.
Example 2
Weighing 10g of PEEK and 80mL of concentrated sulfuric acid, heating in a water bath at 60 ℃ for 4 hours, pouring the reacted solution into ice water to obtain threadlike sulfonated polyether ether ketone (SPEEK), then washing with water until the solution is neutral, and drying for later use; dissolving 1.2g of PAN powder in 10mL of N-N dimethylformamide in a beaker to prepare a PAN solution with the mass fraction of 12% wt, dissolving 2g of SPEEK powder in 10mL of N-N dimethylformamide in the beaker to prepare a SPEEK solution with the mass fraction of 20% wt, measuring 10mL of PAN solution and 6mL of SPEEK solution in the beaker, uniformly stirring to form a uniform solution, weighing 10mL of spinning solution in an injector, placing the injector on a bracket of an electrostatic spinning machine, selecting a high-speed roller as a receiving device, winding a layer of aluminum foil on the roller for receiving polyacrylonitrile/sulfonated polyether ether ketone fibers, connecting a syringe needle with the positive pole of a high-voltage power supply through a lead, connecting the roller with the negative pole of the high-voltage power supply, wherein the platform moving distance is 23cm, the voltage is 21KV, the injection speed is 1mL/h, and the rotation speed of the roller is 120rpm, the receiving distance is 21cm, the spinning time is 10 hours, the spinning temperature is 25 ℃, the humidity is 40%, the diameter of a roller is 23cm, the electrospun polyacrylonitrile/sulfonated polyether ether ketone fiber membrane is taken down from the roller, the electrospun polyacrylonitrile/sulfonated polyether ether ketone fiber membrane is dried in a vacuum oven at 60 ℃ to obtain a primary spinning membrane, then the primary spinning membrane is subjected to hot pressing treatment under a universal tester, the hot pressing temperature is 80 ℃, the pressure is 5MPa, the time is 1min, 2% o-chitosan acetic acid aqueous solution and 2% carboxylated carbon nanotube aqueous solution are prepared, and the battery diaphragm is obtained by self-assembling the hot-pressed membrane in 10 layers.
Example 3
Weighing 10g of PEEK and 80mL of concentrated sulfuric acid, heating in a water bath at 80 ℃ for 6 hours, pouring the reacted solution into ice water to obtain threadlike sulfonated polyether ether ketone (SPEEK), then washing with water until the solution is neutral, and drying for later use; dissolving 1.2g of PAN powder in 10mLN-N dimethylformamide to prepare a PAN solution with the mass fraction of 12% wt in a beaker, dissolving 2g of SPEEK powder in 10mLN-N dimethylformamide to prepare a SPEEK solution with the mass fraction of 20% wt in the beaker, measuring 10mL of PAN solution and 2.6mL of SPEEK solution to stir uniformly in the beaker to form a uniform solution, measuring 10mL of spinning solution in an injector, placing the injector on a bracket of an electrostatic spinning machine, selecting a high-speed roller as a receiving device, winding a layer of aluminum foil for receiving polyacrylonitrile/sulfonated polyether ether ketone fibers on the roller, connecting a syringe needle with a positive pole of a high-voltage power supply through a lead, connecting the roller with a negative pole of the high-voltage power supply, wherein the platform moving distance is 23cm, the voltage is 21KV, the injection speed is 1mL/h, and the roller rotating speed is 120rpm, the receiving distance is 21cm, the spinning time is 10 hours, the spinning temperature is 25 ℃, the humidity is 40%, the diameter of a roller is 23cm, the electrospun polyacrylonitrile/sulfonated polyether ether ketone fiber membrane is taken down from the roller, the electrospun polyacrylonitrile/sulfonated polyether ether ketone fiber membrane is dried in a vacuum oven at 60 ℃ to obtain a primary spinning membrane, then the primary spinning membrane is subjected to hot pressing treatment under a universal tester, the hot pressing temperature is 100 ℃, the pressure is 5MPa, the time is 1min, 2% o chitosan acetic acid aqueous solution and 2% carboxylated carbon nanotube aqueous solution are prepared, and the battery diaphragm is obtained by carrying out 15-layer-by-layer self-assembly on the hot-pressed membrane.
Claims (10)
1. A preparation method of a lithium-sulfur battery diaphragm is characterized by comprising the following steps:
(1) putting polyether ether ketone (PEEK) and concentrated sulfuric acid into a container, heating in a water bath for several hours, pouring the reacted solution into ice water to obtain threadlike sulfonated polyether ether ketone (SPEEK), then washing with water until the solution is neutral, and drying for later use;
(2) dissolving Polyacrylonitrile (PAN) in an organic solvent, stirring at room temperature to form a uniform and stable solution, dissolving sulfonated polyether ether ketone in the step (1) in the organic solvent, stirring at room temperature to form a uniform solution, mixing the two solutions, and continuously stirring until a uniform spinning solution is formed;
(3) weighing 5-15mL of spinning solution in an injector, placing the injector on a bracket of an electrostatic spinning machine, selecting a high-speed roller as a receiving device, winding a layer of aluminum foil on the roller for receiving polyacrylonitrile/sulfonated polyether ether ketone fibers, connecting a syringe needle with the anode of a high-voltage power supply through a lead, connecting the roller with the cathode of the high-voltage power supply, moving a platform at a distance of 15-25cm, a voltage of 18-24KV, an injection speed of 0.5-2mL/h, a roller rotating speed of 100-150rpm, and a receiving distance of 20-22 cm:
(4) taking the electrostatic spinning polyacrylonitrile/sulfonated polyether ether ketone fiber membrane off a roller, drying in a vacuum oven to obtain a primary spinning membrane, and then carrying out hot pressing treatment under a universal testing machine;
(5) preparing a chitosan solution and an aqueous solution of a carboxylated carbon nano tube, and performing soaking method layer-by-layer self-assembly on the membrane obtained in the step (4) in the chitosan solution and the aqueous solution of the carboxylated carbon nano tube respectively to obtain the battery diaphragm.
2. The method according to claim 1, wherein the mass ratio of the polyetheretherketone and the concentrated sulfuric acid in the step (1) is 1: 7 to 1: 9.
3. The method of claim 1, wherein the temperature of the water bath heating in step (1) is 60 ℃ to 80 ℃.
4. The preparation method of claim 1, wherein the water bath heating time in step (1) is 2-6 h.
5. The method according to claim 1, wherein the organic solvent in step (2) is one or a mixture of N-N Dimethylformamide (DMF), N-N dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and Tetrahydrofuran (THF).
6. The preparation method according to claim 1, wherein the polyacrylonitrile in the step (2) accounts for 8-12 wt% of the solution, the sulfonated polyether ether ketone accounts for 15-25 wt% of the solution, and the two solutions are mixed according to the mass ratio of the polyacrylonitrile to the sulfonated polyether ether ketone being 90% -10% -50% to 50%.
7. The preparation method according to claim 1, wherein the spinning time in the step (3) is 1 to 10 hours, the spinning temperature is 20 to 50 ℃, the humidity is 20 to 50%, and the diameter of the roller is 15cm to 25 cm.
8. The method according to claim 1, wherein the drying temperature in the step (4) is 40-100 ℃, the hot pressing temperature is 60-100 ℃, the pressure is 3Mpa-10Mpa, and the hot pressing time is 1min-30 min.
9. The method according to claim 1, wherein the solvent of the chitosan solution in step (5) is one or a mixture of an acetic acid solution, a hydrochloric acid solution and a sulfuric acid solution.
10. The method according to claim 1, wherein the number of the assembly layers in the step (5) is 0 to 20.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113529407A (en) * | 2021-07-13 | 2021-10-22 | 苏州大学 | Layer-by-layer self-assembly material, preparation method thereof and flexible strain sensor |
| CN113937295A (en) * | 2021-10-15 | 2022-01-14 | 山东大学 | Self-assembled MXene/chitosan composite membrane and preparation method and application thereof |
| CN115377606A (en) * | 2022-08-23 | 2022-11-22 | 北京化工大学 | High-performance chitosan/polyacrylonitrile diaphragm for multifunctional lithium-sulfur battery and preparation method and application thereof |
-
2019
- 2019-10-22 CN CN201911003234.0A patent/CN112768834A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113529407A (en) * | 2021-07-13 | 2021-10-22 | 苏州大学 | Layer-by-layer self-assembly material, preparation method thereof and flexible strain sensor |
| CN113937295A (en) * | 2021-10-15 | 2022-01-14 | 山东大学 | Self-assembled MXene/chitosan composite membrane and preparation method and application thereof |
| CN113937295B (en) * | 2021-10-15 | 2023-04-18 | 山东大学 | Self-assembled MXene/chitosan composite membrane and preparation method and application thereof |
| CN115377606A (en) * | 2022-08-23 | 2022-11-22 | 北京化工大学 | High-performance chitosan/polyacrylonitrile diaphragm for multifunctional lithium-sulfur battery and preparation method and application thereof |
| CN115377606B (en) * | 2022-08-23 | 2023-12-12 | 北京化工大学 | High-performance chitosan/polyacrylonitrile membrane for multifunctional lithium sulfur battery, and preparation method and application thereof |
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